Electrochemical Synthesis and Structural Characterisation of Cadmium and Mercury Complexes Containing Pyrimidine‐2‐thionate Ligands

Abstract

AbstractThe electrochemical oxidation of anodic metal (cadmium or mercury) in a cell containing an acetonitrile solution of the appropriate pyrimidine‐2‐thione (RpymSH) affords complexes [M(RpymS)2] (M = Cd, Hg; R = 4‐CF3, 4,6‐CF3,Me and 4,6‐CF3,Ph). When 2,2'‐bipyridine (bipy) or 1,10‐phenanthroline (phen) was added to the electrolytic cell, adducts of cadmium and compounds with these coligands were obtained. All the compounds have been characterised by microanalysis, IR spectroscopy and, in the case of the compounds that were sufficiently soluble, by 1H, 13C and 199Hg NMR spectroscopy. The compounds [Cd(4‐CF3pymS)2] (1), [Cd(4,6‐CF3MepymS)2(bipy)] (4), [Cd(4,6‐CF3PhpymS)2(phen)] (6) and [Hg(4,6‐CF3MepymS)2] (8) were also characterised by X‐ray diffraction. Compound 1 presents a polymeric structure with the polymer chains interconnected by intermolecular C–H···N interactions. Compounds 4 and 6 adopt mononuclear structures, with weak inter‐ and intramolecular C–H···π interactions, as well as π–π stacking interactions for compound 6. Compound 8 also presents a mononuclear structure with intermolecular π–π interactions between the pyrimidine rings and additional weak Hg···Hg contacts (3.484 Å). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)